Stabilized pesticidal compositions



United States PatentO 2,868,688 STABILIZED PESTICIDAL COMPOSITIONS Hans A. Benesi, Berkeley, Calif., Ynn Pei Sun and Erwin S. Loeffler,-Denver, Colo., and Kenneth D. Detling, Orinda, Califl, assignors to Shell Development Company, Emeryville, Califi, a corporation of Delaware No Drawing. Application October 21, 1953 Serial No. 387,512 16 Claims. (Cl. 167--42) This invention relates to new and-improved biocidal compositions of matter. .More particularly, the present inventionpertains'to new and improved insecticidal compositions of matter of the type that are prepared or compounded in the dry, dusty, powdery, or pulverulent form, such as dusts and wettable powders. Methods for preparing the new and improved compositions of the invention are included within the purview of the invention.

Within recent years there have been discovered and in certain cases put into commercial manufacure and use, a number of highly effective synthetic organic toxicants for insects and members of allied classes of animals. Among the most effective of these new insect poisons have been found to be certain polycyclic synthetic organic compounds which are chemically characterized, inter alia, by the presence of chlorine (or other halogen) substitution in the molecule. These highly chlorinated synthetic insecticides can be applied to plants, trees, and other'flora, as well as to other sites of application, by the various methods already known for application of insecticides. For example, a solution or suspension of the toxicant may be sprayed, or a dust comprising the toxicant adsorbed on or in admixture with a solid carrier may be dusted over the area to which the toxicant is to be applied. The dustsordinarily are prepared by the formulator, who then sells and ships the composition ready for use. For orchard, field-crop and other large-scale applications by spraying, the toxicant frequently will be put up in the form of a dry powder containing wetting agents, dispersing or suspending agents, and other adjuncts, for

shipment in the dry or solid state-to the consumer who providing material savings both in formulation and shipment of the compositions, relative to formulation-and shipment of liquid compositions, certain heretofore .unexplained difficulties have been encountered when the abovementioned polycyclic halogen-substituted toxicants have been put up in the form of dusts or wettable powders. There have been several instances where the wettable powder, after bagging, has ignited spontaneously, with substantial loss of property including, of course, 'the de- 1 contain as much as 50% or more by weight of the organic halogen-containing toxicant, the balance beingfthe carrier dust, suspending agents, and the like, and :since there has been observed no material loss of weight of .the insecticidal composition, it has been clear that 'in these latter cases there has occurred a chemical conversion of the toaicant to a non-toxic material, rather than, say, mere 'loss of the toxicant by'volatilization. The problem appears to be one that is peculiar to the dusts, wettable powders, and similar pulverulent compositions for'the :reason that in the pure state the same toxicants in most cases will be substantiallystable.

111 accordance with thepresent invention there are pror ce vided new and improved dusts, powders, wettablepowders, and like pulverulent solid biocidal compositions which overcome the difficulties heretofore encountered and indicated herein. The compositions of the invention comprise the toxicant of the class herein defined, afinelydivided carrier dust, diluent, extender, or carrier of the types employed prior to our invention as an ingredient of dusts, wettable powders, and like pulverulent compositions, and certain adjuncts which we have found impart a high degree of stability to the formulated compositions. The adjuncts which are incorporated in the pulverulent insecticidal compositions according to the invention are certain basesand basic-acting materials. The bases and basic-acting materials which we employ may be referred to as mobile, or dilfusible, bases and basic-acting materials, that is to say, bases and basic-acting materials which upon incorporation with the finely divided carrier, diluent, extender, or filler, difiuse throughout the composition and onto the surfaces of the individual solid particles of the carrier, diluent, extender, or filler. While we do not intend to be bound by any proposed theory, 'it is believed that the base or basic-acting material serves to inhibit a certain catalytic action of the finely divided carrier upon the toxicant present in the composition, and, further, that this inhibition is brought about by' neutralization of certain acidic sites which are on the surface of the individual particles of the carrier and to which such catalytic action is attributable.

The 'wettable powders, dusts, and like pulverulent insecticidal compositions with which the invention is 'concerned contain the toxicant intimately mixed with or in some cases adsorbed on a toxicologically substantially inert filler or diluent, suchas a talc, clay, dia'torna'ceou'searth, calcium silicate, silica, alumina, pyrophyllite', calcite', -or mixtures of the same or otherfin'ely divided solid material. We have discovered, and this discovery forms one of the elements of our invention, that the above-described problems which have been encountered; in the formulation of dusts and wet'table powders containing highly chlorinated (halogenated) polycyclic toxicants is traceable in part to the type of diluent or filler that is used with the highly chlorinated toxicant in formulating the insecticidal composition. More particularly, we have discovered that the instability, of a degree sufiicient to lead to spontaneous ignition of. the composition under appropriate circumstances, is attributable in large part to the particular diluent or filler that is employed, and especially to be related to a property of the solid diluent or filler which conveniently may and will be referred to herein as the intrinsic acidity.

For purposes of explaining and defining the term intrinsic acidity as applied to these solid diluents and fillers, it is necessary to outline briefly certain aspects of the more modern concepts of acid-base relationships insofar as they are pertinent to an understanding of our invention.

When an acid is dissolved in water it will form a solution having an acidity, or pH value, that is determined solely by the concentration and the acidic strength .of the particular acid. The acidity of the solution is determined by the extent to which the reaction:

proceeds to the right, that is, by the tendency of the particular acid, AH, to react with the water yielding the conjugate'base or anion, A-f, of the .acid and the oxonium ion. For dilute aqueous solutions the acidic strength of the acid can be defined by the ionization constant, K which is the equilibrium constant for Reaction 1:

a! the parentheses indicating concentrations of the respectrve ionic and molecular species. The acidity constant can be expressed in terms of the pK value of the acid which is related to the acidity constant by the equation:

From these relationships, it will be apparent that, the stronger the acid the higher will be the numerical value of the acidity constant K and, conversely, the lower will be the numerical value of the corresponding pK va ue.

It will be evident that the reaction of the acid HA with water to form the conjugate base A- and the oxonium ion can be considered to be the sum of two separate reactions; firstly, the ionization of the acid to yield the anion A- and the hydrogen ion H+ and, secondly, the hydration of the hydrogen ion.

It thus will be seen that the extent to which the reaction represented by Equation 1 will extend to the right at equilibrium is determined not only by the tendency of the acid to undergo dissociation according to the reaction represented by Equation 4, but also by the basicity of the water, or its afiinity for the proton. The range of acidity constants which can be measured in water is limited by reason of the basicity-of the water. Thus, with different acids of progressively increasing acidic strength, there is found a limiting group of acids which, in water, ionize to such an extent according to Equation 1 that the respective concentrations of the undissociated acid HA are too small to detect and the acids are commonly referred to as being completely dissociated. These acids are also referred to as the strong acids. They are typifiedby HCl, HBr, HC1O and in water are indistinguishable from each other in acidic strength. Thus, owing to the basicity of water, and the prevalence of aqueous systems, it has been common to regard the possible range of determinate pK values as being limited to positive numerical values.

It will be seen from further consideration of Equations 1, 4, and 5 that, if there is substituted for the water a material B which is less basic (has less affinity for the proton) than does water, there will be less tendency for the reaction to proceed to the right than when water, instead of B, is present as the proton acceptor. It thus is conceivable that, by employing suitable non-aqueous systems, there will be found to exist materials which, although having pK values which are indeterminable in aqueous solutions, have pK values which can be ascertained when appropriate measurements are carried out in the presence of only such less basic materials. This indeed has been found to be the case, and it has been found that there are a number of materials whose acidity constants are beyond the scale that is determinable in an aqueous system.

For measurement of these hyperacidities, as the acidity constants beyond the scale determinable in aqueous systems may be referred to, we take advantage of the fact that there are a number of electrically neutral bases, less basic than water, which exhibit a color change upon reaction with an acid, that is, upon acquisition of a proton. Thus, upon mixing the neutral base B with an acid AH the base acquires a proton from (is neutralized by) the acid and the transition from B to BH+ results in a visible change of color. The extent to which the base B will combine with the acid HA depends upon the strength of the base aswell as upon the strength of the acid. With decreasing basic strength (decreasing affinity for the pro- B) BH'i') in which pK is the acid ionization constant for the conjugate acid BH+ of a neutral base B, referred to dilute aqueous solutions. It will be seen that the intrinsic acidity of an acid is numerically equal to the acid ionization constant for the conjugate acid of a neutral base which, in contact with the acid, is caused to exist one half Intrinsic acidity=pK =pK +1og in the form of the conjugate acid BH+ of the base B.

A limited number of neutral bases (proton acceptors) are known (1) to be sufficiently weak bases to be neutralizable by acids having acidity constants in the region of hyperacidity and (2) to show a visible change of color upon such neutralization. Hammett, L. P., Physcal Organic Chemistry, McGraw-Hill, 1940 (New York), page 266. Illustrative of such indicators which we may use are the compounds that are listed in the following table with the acid dissociation constants (pK for their respective conjugate acids.

Indicator pK nn+ Neutral Acid Color Color p-dimethylamlnoazobenzene +3 1 yellow red. 2-amino-5-azotoluene +2. 2 d orange. benzeneazo'ltohenylamine +1. red-purple. dtcinnamal cetone 2 red. b nz tl ic to h none yello anthmquinone o.

It may be noted that benzalacetophenone, with a pK equal to 5.6, does not change color in aqueous sulfuric acid solution until the strength of the solution exceeds 70% H 50 and that a concentration of approximately H 50 is required in order to convert anthraquinone into its colored, conjugate acid.

We have found that the intrinsic acidity of the solid diluents, carriers, extenders, or fillers which are used for formulating dusts, wettable powders, and similar pulverulent insecticidal compositions can be determined by applying to it, either before or after incorporation of the toxicant, a small amount of a solution in an organic solvent of an indicator having a previously determined pK value and observing the color of the solid containing the adsorbed indicator compound. For example, we have found that, when a small amount of a benzene solution of dicinnamalacetone, is applied to Attaclay, a commercial insecticidal carrier composed of finely ground atta'pulgite, there is observed a development, from the almost colorless solution, of a deep red color on the clay. This observation reveals two important facts; firstly, that the surface of the clay is reacting with the dicinnamalacetone in the same way that an acid reacts with it and, secondly, that the surface of the clay is acting as an acid having suflicient acidic strength to convert the dicinnamalacetone to its colored, acidic form. By employing a series of indiactors with known acid dissociation constants, and by observation of the colors when separate samples of the carrier material are treated with the respective indicator solutions, the intrinsic acidity of the carrier material can be substantially quantitatively ascertained. We have discovered, and

this discovery forms a further element of our invention, that various materials heretofore widely used as supposedly inert diluent or carriers in the formulation of insecticidal dusts and carriers have surprisingly high intrinsic acidities, and that the stronger is the intrinsic acidity of the The-strength of the intrinsic acidities that'are involved can be readily illustrated by specific figures. Representative samples of Attapulgite clay, whendried at 120 C. and then testedin the manner described above, react basic when tested with benzalacetophenone and acid when tested with dicinnamalacetone, evidencing a pK value for the Attapulgite clay between about 2 and about 5. When a typical kaolin is tested similarly, it reacts acidic to all of the indicators-listed above except anthraquinone, to which it is mildly basic. These observations indicate a pK value between .5 and -8 for the kaolin. The strength of the acidities represented by these figures will be better appreciated when it:is understood, as we have .observed,.that addition of asmall amount of benzalacetophenone to aqueous sulfuric acid solution yields the yellow color typical of the acidic .reaction of thisindicator only when the solution hasa sulfuric acid concentration of 70% or more. Anthraquinone, which is but partly neutralized by the kaolin, shows an acidic reaction, upon addition to sulfuric acid, only when the sulfuric acid has a concentration of 90% or more H 80 The intrinsic acidities of the diluents or carriers which are employed'in the insecticidal compositions can be conveniently determined by applying a small amount of a solution of the indicator compound in an inert, neutral organic solvent, such as benzene or iso-octane, to the carrier or diluent or to the insecticidal composition containing the carrier or diluent, the material to be tested being either in .the drystate or moistened with a further quantity of the solvent. Indicator solutions containing 0.2% by weight of the indicator compound are suitable. 'When a small amount of dry, finely ground kaolin is spread on a piece of white paper and a drop or two, for example, of p-dimethylaminoazobenzene solution in benzene is dropped onto the clay, the spot moistened by the solution instantly turns a brilliant crimson indicating that the indicator is present in its acid form on the clay. When theindicators listed in the above table are applied to different portions of the kaolin, each of the indicators through benzalacetophenone develops the typical acid color indicating that the kaolin has a pK value lower than the pK value of the indicator. Instead of applying the indicator solution to the dry material that is to be tested, a small amount (e. g., 0.1 to 0.2 gram) may be placed in a test tube, a cubic centimeter or so of benzene added, and the indicator solution (one or two drops) added, whereupon the solid acquires the color characteristic of the indicator and the pK value of the solid.

The intrinsic acidities which have been discussed above are to be clearly distinguished from the acidities of the carrier materials as measured by the conventional technique of suspending the carrier material in water to form a paste or suspension, and determining the pH value of the paste or suspension. Indeed, there appears to be no observable correlation between the intrinsic acidity of a carrier or diluent and its acidity as determined by this latter method. This will be further seen from the experimentally determined values which are given in the following table:

The values shown in the, preceding table for Diluex emconcerned, to undergo loss oftoxicity or even vigorous decomposition.

1phasize the distinction between the intrinsic acidity .and

the acidity-as determined by measurement of l the: pH of, a

suspension of the. solid diluent-in water. While theyaqueous suspension of Diluex showed a pH of 9.2, whichrepresents -a mildly alkaline -solution,the intrinsic .acidity'of Diluex was found'to correspond to a pK value of -5,

. and an acidicstrength approximately equivalent to that of a 70% "solutio-n'of H -We have now discovered, and this discovery forms a further and important element of our invention, that .fuse or permeate the pulverulent composition and thereby *to'reach and to react or'combine with, or neutralizethe surfaces of the individual minute solid particles of the or blending, or storage'of the biocidal composition.

.Bases and basic-acting materials which can be employed include materials which, although in themselves not free bases or alkalies, have an alkaline reaction or basicit-y,

. and materialswhic'h, although in themselves substantially non-basic, decompose under the conditions encountered in'the grinding, mixing, blending 'orsubsequent storage to yield in .situ a mobile base or basic-acting material.

The'materials which we may'employ as such bases, basic-acting materials, and progenitors of bases or basicacting materials maybenormally either liquid, solid, or gaseous. However, the materials which are normally solid and have an appreciable'volatility offer'certain advantages .fromthestandpoint of ease of incorporation-in the solid pulverulent biocidal compositions as well as a generally more eifective andlonger lasting stabilizing action, and hence are to be preferred.

' operations, and that the progenitor, if 'a progenitor .in

solid form is employed, decompose under such conditions to produce an appreciable vapor of a base or basic-acting material. The vapors thus generated in the blended composition appear to suifuse the individual particles, entering the pores and interstices of the individual particles and neutralizing or combining with the acidic sites which give rise to high intrinsic acidity. It is to be noted inthis respect that a dry non-volatile base or basic-reacting material, when blended into or intimately mixed in finely divided state with dry mixtures of the halogenated toxicants with which the invention is concerned and a solid pulverulent diluent having a high intrinsic acidity, does not impart stability to the composition. It appears from our studies that the dry non-volatile base or basic-acting material lacks the requisite mobility, or diffusa bility, and that by reason of this lack it is incapable of reaching and combining with or neutralizing acidic sites on the exterior and within the interstices or pores of the individual particles of the solid diluent, carrier, or filler, with the result that stability as.rea1ized by'the practice of the present invention is not attained.

On the other hand, we may employ substantially nonvolatile basic-acting materials in the form of solutions. For example, an alkali, such as sodium hydroxide or potassium hydroxide, or an alkaline salt, such as sodium carbonate, may be applied to the solid carrier by forming a slurry of the solid carrier in a solution-'of'the basicacting material, thereby neutralizing the intrinsic acidity of the surfaces of the carrier, and then washing and drying the treated carrier. Thereafter the toxicant and other 7 components of the desired pulverulent biocidal composition may be suitably incorporated with the treated carrier dust, as by grinding, to yield a stable composition of our invention.

The base, basic-acting material, or progenitor, when applied in liquid form, may comprise a solution in water or an organic solvent of a solute which is normally gaseous, normally liquid, or normally solid, or the base, basic-acting material, or progenitor may be a single substance which itself is liquid at the temperatures involved. Volatile bases and basic-acting materials which can be employed in liquid form include, for example, ammonia, ammonia applied as an aqueous ammonium hydroxide solution, and lower alkylamines such as methylamine and ethylamine. Bases which are normally liquid and may be applied as such or dissolved in a solvent include higher alkylamines such as isopropylamine, propylamine,

hexylamine, amylamine, isoamylamine, undecylamine, triethylamine, and homologous and analogous mono-, di-, and trialkylamines. Cyclic amines may also be employed, such as the aromatic amines aniline, N-methylaniline, diphenylamine, beta-phenylethylamine and naphthylamine, as well as heterocyclic amines such as piperidine, 2,2,4,6- tetramethylpiperidine, pyridine, tetrahydropyrimidine, and morpholine, and alicyclic amines, such as dihexylamine, and 3,3,S-trimethylcyclohexylamine. Polyamines may also be used, such as ethylenediamine, diethylenetriamine, triethylenetetramine, and hexamethylenediamine, as well as substituted amines such as ethanolamine, diethanolamine, triethanolamine, 2-hvdroxy-l,3- prop anediamine, N- 3-amino-2-hydroxypropyl -3 -amine- 2-hydroxypropylamine, 3-chloro-Z-hydroxypropylamine, and the like and their homologs and analogs.

From the standpoint of ease of preparation, their stability, and durability, the most desirable compositions of the in ention are those which comprise the pulverulent inert diluent, filler, or carrier, thetoxicant of the class with which the invention is concerned, and in intimate admixture therewith a solid, finely divided, appreciably volatile base or basic-acting material or progenitor of an appreciably volatile base or basic-acting material. The base, basic-acting material, or progenitor advantageously may be any compound which over the range of from about normal temperatures, say, 25 C. to about 150 C., decomposes either by simple thermal decomposition or by acid-catalyzed decomposition to yield ammonia or one of the normally gaseous lower homologs of ammonia, that is to say, a lower volatile alkylamine. The preferred materials of this type which are employed in the compositions of the invention are the amides of carbonic acid and salts of carbonic acid with nitrogen bases, including without being limited to ammonium carbonate, ammonium bicarbonate, ammonium carbamate, urea, methylurea, ethylurea, methyleneurea, acetylurea, sodium allophonate, ethyl allophonate, thiourea, and isothiourea. Guanadine may also be employed, as may salts of guanadine, such as guanadine carbonate. Further solid progenitors which we may employ include hexamethylenetetramine, melamine, cyanamide, and substituted ureas, such as methylurea, triethylurea, ethylideneurea, and trimethyleneurea.

We have found it to be particularly desirable that the base, basic-acting material, or progenitor be one which has a melting point above and not too near the normal or ambient temperatures, yet which has sufiicient volatility or tendency to decompose to yield ammonia at temperatures within the range normally encountered during grinding, blending, mixing, packaging, and storing the biocidal'compositions. Of particular value have been found to be urea, ammonium carbamate, ammonium carbonate, and ammonium bicarbonate. They may be used individually or mixtures of any two, three or of all four may be employed.

The toxicants which are employed in the improved compositions of the invention are the organic halogen- -may be of a different ring size.

8 containing (chlorine-containing) biocidal compounds which contain a plurality of atoms of halogen (chlorine) and a plurality of rings at least two of which are fused together and at least one of which rings that are fused together is substituted by halogen (chlorine). When reference is made to rings that are fused together, or to a fused ring system, reference is intended to the structure in which at least two rings of atoms are directly attached to each other with two or more carbon atoms being common to each of the rings of a fused pair of rings. For example, indene 4 E3 3 a t a 6110 C CH 2 C OH H 1 has but one carbon atom common to the two rings and, therefore, does not contain a fused ring system. In the fused ring system of the toxicants which We employ, the respective rings may be of the same size, i. e., both may be hexatomic, heptatomic, pentatomic, tetratomic, etc., or one ring may be of one size and a ring fused therewith Thus, the biocides with which the invention is concerned may be described generically as containing the structure /I\ R (C), R

in which R and R are divalent radicals which, together with the carbons form a fused ring system and x represents 0 or a small Whole positive number, and in which at least one of the two rings depicted by theformula is halogen (chlorine) polysubstituted. The divalent radicals represented by R and R may be linear unsubstituted acyclic hydrocarbon groups, such as the methylene, ethylene, propylene radicals and their alkyl and/ or chlorinesubstituted analogs, e. g., Z-methylpropylene, 1,2,3-trichloropropylene, or 2-bromopropylene, or they may be unsaturated, as for example, the 1,2-dichloroethenylene radical (--CCl=CCl), the ethenylene radical (CH=CH) the 2-butenylene-1,4 radical (CH CH=CHCH the 2,3-dichloro-2-butenylene-l,4 radical (CH CCl=CClCI-I the hexachloro-Z-butenylene-1,4 radical (CCl CCl=CClCCl the l-chloro-Z-propenylene-l,3 radical (--CHC1CH=CH) and the 2-chloro-2-propenylene-1,3 radical (CH -CCl=CH-) R are as follows:

I aea The groups represented :R' and: R may be the same 1 or theymay be different, andone or both may comprise in itself a ring structure; for example, one orhoth, of the :g'roups represented by R and, R; may be a 4cycloheXen-- =ylene1,2 radical f a '3fi rnethano i ycloheitenylene l radical a 3-cy'clopentei1ylene-1 ,2 radical in which R and R each represent a divalent radical as defined above and each X represents an atom of halogen.

Each X can be bromine or chlorine; in the best known toxicant's of the group defined by this formula each Xj-is chlorine and R represents the dichloroethenyleneradical (-CCl=CCl). R generally is a pentatomic carbocyclic ring which'in itself may be either unsubstituted,

or substituted by halogen (chlorine), or a member of a group of fused pentatomic rings, as in the formula when'x has a positive integral value. In this latter formula for the general case x represents 0 or a small whole positive number, and M and P represent separately hydrogen, halogen (chlorine), or hydroxyl, and together the ethenylene group, the ethylene group, or an epi-substituted ethenylene group wherein the epiatomic component may be selected from the class consisting of epoxy, ep'isulfido, and episulfoxy.

To xicants to which the principles of the invention are primarily applicable for preparing new and improved pulverule'nt insecticidal compositions include, for example, aldrin, which is the 1,2,3,4,10,10-heXachloro-1,4,4a,

5,8,8a-hexahydro 1,4,5,8 dimethanonaphthalene having the stereochemical configuration of the product of Diels- Alder r'eaction of hexachlorocyclopentadiene and bicycle- (2.2.1)'-2,5-heptadiene and which can be prepared by such reaction, and the stereoisomer of aldrin, namely, isodrin, which 'is the 1,2,3,4,l0,10-hCXflChlOlO-1,4,4fl,5,8, 8a-hexahydro-1,4,5,B-dimethanonaphthalene having the stereochemical configuration of the product of Diels- Alder reac tio'nof cyclopentadiene and 1,2,3,4,7,7-hex'achlorobicyclo(2.2.l )heptadiene-2,S and which can be prepared by such reaction.

Other toxicants to which the principles of the invention are similarly applicable are Endrin, the 1,2,3,4,l0',10- heXachloro-1',4,4a,5,8,8a-hexahydro 6,7 epoxy 1,4,5 ,8- dimethanonaphthalene which is the epoxide of isodrin; die ldrin, the l,2,3,4,10,10-heXachloro-1,4,4a,5,8,8a-hexahydro-6,7-epoxy-1,4,5,8 dimethanonaphthalene which is the epoXide of aldrin; l,'4,5,8,9,lO-trimethano-l,2,3,4,13, 13-hexachloro-1,4,4a,5,6,7,8a,9,9a,10, IOa-dodecahydroanthracene, 1,2,3,4,6,6,10,10 octachloro 1,4,4a,5,6,7,8,8aoctahydro-1,4,5,8-dimethanonaphthalene, 1,2,3,4,6,10,10- heptachloro 1,4,4a,5,6,7,8,8a octahydro-1,4,5,8-dimethanonauhthalene, 6-phenyl-1,2,3,4,10,10-hexachloro-1,4,4a, 5,6,7,8,8a-octahydro-1,4,5,S-dimethanonaphthalene, 6 acetoXy-1,2,3,4,10,10-hexachloro 1,4,4a,5,6,7,8,8a octahydro- 1,4,5 ,8-dimethanonaphthalene, 6-keto-1,2,3,4,6,10,l0- hexachloro-1,4,4a,5,6,7,8,8a-octahydro-l,4,5,8-dimethanonaphthalene, 6,6,7-trimethyl-1,2,3,4,6,10,10 hexachloro-1, 4,4a,5,6,-7,8,8a octahydro-1,4,5,S-dimethanonaphthalene, 6-ethyl-7-methyl-1,2,3,4,6,10,IO-hexachloro-l,4,4a,5,6,7,8, 8a-.octahydro-1,4,5,8-dimethanonaphthalene; the dodecachlorohexacycloheptadecadiene (C H Cl which is produced as the infusible solid Diels-Alder adduct of bicycle- (2.2.1)-2,5-heptadiene with 2 moles of hexachlorocyclopentadiene; the dicarbethoxyhexachlorotetracyclododecadiene (C H O Cl Which is obtained as Diels-Alder adduct of 2,3-dicarbethoxy-2,S-heptadiene (the Diels- Alder adduct of diethyl 'maleate and cyclopentadiene) and hexachlorocyclopentadiene; the dioxohexachlorotricyclononadecadiene which is obtained by Diels-Alder reaction between hexachlorocyclopentadiene as the diene and 1,4-benzoquinone as the dienophile; the hydroquinone isomerof said dioxohexachlorotricyclononadecadiene; chlordane, or 'Octachlor, which is 1,2,4,5,6,7,8,8-octa- -chloro-2,3,3a,4,7,7a-heXahydro 4,7 methanoindene; including, specifically, the various stereo'chemical isomers which are comprehended by the planar structure named heptachlor, or 1 (or 3a), 4,5,6,7,8,8-heptachloro-3a,4,7,

p7a-tetrahydro-4,7 methanoindene; compound 601, or 1,

' 11 2,3,4,7,7-hexachlorobicyclo-(2.2.1)heptadiene 2,5; hexabromotetracyclododecadiene formed as Diels-Alder adduct of hexabromocyclopentadiene and cyclopentadiene; the stereoisomeric episulfides of isodrin and aldrin, respectively, each having the planar structure represented by the name 1,2,3,4,l0,lO-hexachloro-1,4,4a,5,6,7,8,8a-octahydro-6,7-episulfido-1,4,5,8-dimethanonaphthalene; chlordene, or 4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahydro-4,7- methanoindene; 1-hydroxy-4,5,6,7,8,8-hexachloro 3a,4,7, 7a-tetrahydro-4,7-methanoindene, or l-hydroxychlordene; HCA bromides, such as 1(or 2-)-bromo4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene; and HCA epoxides, such as 1,2-epoxy-4,5,6,7,8,8-hexachloro-3a,4,7, 7a-tetrahydro-4,7-methanoindene.

Further examples of toxican'ts with which the principles of our invention are applicable are the chlorinated polycyclic terpenes containing fused alicyclic rings. The carbon atom or atoms which are common to the two rings may be substituted by methyl groups or chloromethyl groups, as in chlorinated alpha-pinane, chlorinated camphane, or chlorinated alpha-pinene, or the bridge carbons may be unsubstituted by other than hydrogen or chlorine, as in the probable structure of chlorinated camphene. The chlorinated terpene may be one prepared by chlorination of a relatively pure compound, for example, toxaphene, or chlorinated camphene, or it may be a chlorinated mixture of terpenes, as, for example, strobane.

The principles of our invention are applicable to the formulation of new and improved biocidal compositions of matter with the aid of any of the customary diluents, carriers, extenders, or fillers which are useful for the formulation of pulverulent dry insecticidal dusts, wettable powders and the like. Of primary importance, of course, are the compositions of the invention in which the carrier, diluent, extender, or filler is one which normally is characterized by high intrinsic acidity. In this case the problem of instability of the formulated composition is directly overcome and new, useful, stable compositions are obtained, which are highly toxic at the outset and retain their toxicity under conditions highly detrimental to the compositions known prior to our invention. However, it will be readily understood by those skilled in the art that the application of the principles of our invention is not correspondingly limited. For example, a dust or powder containing a toxicant of the class defined herein and a nonacidic pulverulent mineral carrier or diluent may be prepared with incorporation of urea, ammonium bicarbonate, or ammonium carbarnate. By reason of the presence of the nitrogenous component, the composition tends to be protected against decomposition should the composition be subsequently inadvertently or intentionally blended or diluted with an'intrinsically acidic diluent, such as attapulgite or kaolin.

The carriers, diluents, or extenders with which instability of the halogen-containing fused-ring polycyclic toxicants is encountered are primarily those which have an intrinsic acidity stronger than is represented by a pK value of about determined as described herein. The problem of instability of the formulated insecticidal composition has been found to be particularly acute when the carrier, dried at 120 (3., is one having an intrinsic acidity greater than a pK value of about -2. We have found that many clays, in particular, are characterized by objectionably high intrinsic acidity, and of the clays those of the kaolinite group, specifically kaolinite, nacrite, dickite, and anauxite, and those of the attapulgite group, such as attapulgite and sepiolite, warrant particular mention. Less strongly acidic carriers or diluents which can be employed for preparing the new and improved compositions of the invention include, among others, the montmorillonite clays, such as montmorillonite, saponite, montronite, and beidellite, and other silicates, such as talc, mica, and pyrophyllite, sulfates, such as gypsum, and carbonates, such as calcite and dolomite. The carriers or diluents can be employed singly or mixtures may walnut shell and other botanical flours, diatomites,' e1 emental sulfur, and the like. I

The amount of themobile, or perfusable base, basicacting material, or progenitor which is incorporated in the biocidal compositions of our invention may be varied, within limits, according to the intrinsic acidity of the pulverulent carrier or diluent, as well as according to the amount of the carrier present in the composition. The amount should be sufficient to at least substantially neutralize the intrinsic acidity of the carrier or diluent. Whether the intrinsic acidity has been neutralized can be determined conveniently by measuring the apparent pK value of the complete biocidal composition (or of a mixture of the carrier or diluent and the base, basicacting material or progenitor) with the aid of p-dirnethylaminoazobenzene or equivalent indicator. Compositions prepared according to ourinvention which register an apparent pK value not stronger than about pK +3, or wherein a mixture of the carrier or diluent prior to incorporation of the toxicant registers a pK value not stronger than about pK +1,'generally can be expected to be completely stable in blending, grinding, storage, packaging, and shipment, while even compositions which have been brought only to an apparent pK value of 0 will show a marked improvement in stability over the corresponding compositions known only prior to the invention. When the composition is one comprising endrin as toxicant, it is preferable that the carrier dust be neutralized to a pK value of from 4 to 5.: When we refer to neutralization, we mean neutralization' to a measured pK value not less than pK 0, as distinguished from the perhaps more usual reference to neutralization of an aqueous solution as meaning to a hydrogen ion concentration represented by pH 7. The minimum amount of the base, basic-acting material or progenitor required for neutralizing the intrinsic acidity, while depending upon, inter alia, the equivalent weight of the base, basic-acting material, or progenitor, generally will be between about 0.05% and about 10% by weight of the pulverulent carrier or diluent. Amounts over about 10% by weight of the pulverulent carrier or diluent ordinarily are unnecessary, although as much as 25% or more, same basis, of the base, basic-acting material, or progenitor may be employed if desired.

The compositions of our invention can be prepared by the customary methods of the art for preparing pulverulent solid biocidal compositions. If the mobile, or perfusable, base, basic-acting material, or progenitor is to be applied in liquid form, the liquid is sprayed onto the filler, extender, diluent, or carrier while grinding, mixing, or blending. When a gaseous base, such as gaseous ammonia, is to be applied, we incorporate it preferably by grinding, mixing, or blending the solid carrier in closed equipment in an atmosphere containing the gaseous agent. The normally solid bases, basic-acting materials, and progenitors are most easily incorporated singly by grinding, dry-mixing, or blending them into the insecticidal composition. The base, basic-acting material, or progenitor can be incorporated prior to, concurrently with, or after the incorporation of the toxicant and/or other adjuncts. When a progenitor, such as urea, is incorporated, which decomposes only slowly at normal temperatures, we may preliminarily mix it with the pulverulent carrier or diluent and allow an aging period, say a few hours or more, prior to incorporation of the toxicant. In this way, adequate permeation of the individual particles of the carrier or diluent is ensured and any possibility of localized inadequate neutralization is obviated.

The dusts and wettable powders of our invention can be prepared with the aid of adjuvants of types well-known to those skilled in the art such as wetting agents, sticking agents, dispersing agents, or defiocculants, and the like. As sticking agents we may use casein, gelatine, cellulose 3 position.

dieldrin. I

successively in a hammer mill and an air mill until, when.

Intrinsic Acidity ro;

,derivatives such'as carboxy-methyl cellulose, s'ulfite waste liquor, a guru, awater-dispersible synthetic resin, mineral oilgorequivalent adhesives :ll of-which are well-known in-the art, Wetting'agents and dispersing agents which -rn ay be employed include the various naturally occurring 'or synthetic surface-acting materials'known for the purpose, such as, inter alia, soaps saponins, lecithins, fatty acid salts, long-chainalcohols, sulfonated aliphatic and/ or aromatic hydrocarbon derivatives, hydroxy, esters, such assorbitan monolaurate, pine oil, andthe like.

' In the'biocidal compositions of our invention the polyhalogeno-substituted fused-ring polycyclic toxicant may be present; as the sole toxic agent. Usefulcompositions can alsobe prepared according to the invention containing a plurality of such toxic agents. In conjunction j therewith there maybe employed other insecticidal agents of}iiiatural or synthetic, of mineral or organic origin, among which come into consideration sulfur, copper arsenate, pyrethrum, allethr'in/DMC, HETP, malathon,

DDT, BHC, lindar'ie, and others 'weirknown to. those skilled in the art. For dusts, which are to be applied to the habitats'o'f the insect in dry form, the composition rdinarily will contain frorniabout 1 to about by weightof the toxicant while for wettable powders, which. .are applied as a spray after dispersing in water the content of toxicant in the pulverulent compositioncan be as 'igh as 50%, 60% or even 75% by weight of the coin- The following examples are presented for the purpose of illustrating certain of the specific modes' -ofapplying the principles of our invention; It will be appreciated that there are other specific embodiments of the invention than those that are shown in the examples and, there- 'f'ore,.tha't the invention should not be misconstrued as beinglimited to the particular embodimentsof the'examples.

Example 1 i ..pany. It is a finely powdered grade of attapulg ite clay,

or Attapulgus fullers earth, characterized by a bulk density of from about 27 to 31 pounds per cubic foot and an average particle size of about 1 to 2 r'nicroiis.

14 Attaclay, dried at 120 0., when tested by theindiqatdr method 'de'scribed herein, exhibits: an intrinsic acidity represented by a pK value of about PK 5; ;:As noted previously herein, an aqueous. suspension. of Atta-' clay exhibits a pH value of about 7.2 or, in other'words, is essentially neutral. Lot 'A, after tlie two-weeks"storage at 150 F.,.was found to-have retained its initial toxicity to insects, to be readily suspendible in water, and. to be non-phytotoxic, Lot B, at the end of the storage period, was substantially non-toxic to insects.

7 Example 2 r I This example illustrates a composition of our invention containing ammonium. bicarbonate. The'co'rnposi- Two ,dilferent lots of dieldrin dust concentrates were prepared. The first lot (A) was prepared by blending together Attaclay and 5% of urea, based on the weight of Attaclay. When the urea and Attaclay had been thoroughly mixed technical dieldrin (1,2,14,10,10- hexa'chloro 1-,4,4a,5,8,8a hexahydro 6,7 epoxy- 1,4,5,S-dimthanonaphthalene; 97% purity) was added to give a mixture having a 25% by weight content of The well-blended mixture then was ground.

tested by the wet sieve method, 99.5% passed through U. S. No. 325 sieve. The second lot (B) was prepared in an identical manner except that the urea was omitted;- Fifty-pound bags of each of the two lots of dust con-- centrate then were stored at 150 E, which approximates temperatures attainable in railway box 'cars during thesummer. Samples of the compositions were withdrawn after one week andtwo' weeks storage, and the content of dieldrin was determined, The following results were observed:

Lot A Lot B Percent Decomposition cf Dieldrin:

After 1 week at 150 F After 2 Weeks at 150 F After 1 week at 150 F.' After 2 weeks at 150 F a Not determined.

50 1n water. 1

tion was prepared in the same manner as lot in Example 1 except that an equal weight of ammonium bicarbonate was substituted for the urea. When tested in the manner described in Example 1, the composition difference is one that deserves consideration when it: is

desired to employ wetting agents, deflocculants, or the like, which would be adversely affected by excessive alkalinity. The pH of an aqueous suspension of a cornpo'sition such as lot A, Example 1, ordinarily will be 'between about pH 4 and about pH -8.

Example 3 While thoroughlyblending, 5% by weight of a 20% by weight aqueous solutionof ammonia wassprayed onto Attaclay. After the mixture .was thoroughly blended, dieldrin was added to yield a mixture containing 25% weight dieldrin. Themixture was tho-roughly blended and ground to pass a ,U. S. No. 325 sieve. A 50-pound bag of the dust concentrate was stored two weeks at 150 F., during which time there was no observable-decomposition of the dieldrin. The dust conc'entrate, at the end of the storage time, had retained its initial toxicity, was nonphytotoxic, and was readily suspendible The intrinsic acidity of the dust concentrate of this example corresponded to ap'K yalue of about K' +1.5. 1 p

Example 4 Illustrative composi ions of our invention par'ticularly adapted forsuspending in water to yield a spray are shown in the following table: r a

' Percent by Weight Ingredient i-n 4-13 4-0 4-D Dieldrin,.technical 97% purity) 52. 7 51.6 51.6 51.0 Dup nal M, dry 1.0 1.0 1.0 1.0 Marasperse OB 5.1 5.0 5.0 5. 0 Sodium tripolyphosphate. 1.0 .1. 0 v1.0 1. 1) At clay 40.2 39 4 39. 4 39. 4 Urea l 2.0

NTlHCOw 2.0 20% aq. NH4OH solution K 2.0

' Total 100. 0 100. 0 100. 0 100. 0

Dispersing agent; sodium salt of technical lauryl'alcohol sulfate; E. I. d'i Pont de Nemours and Comp ny. v

b Dispersant; partilly desulbnated sodium lignosulfonate; Marathon Corporation.

.15 centration of 0.625% by weight. The actual dieldrin concentrations of the suspensions were determined analytically and found to be as follows:

Wettable Powder 4-A Suspendability, percentmn' The results show that, within the limits of accuracy of the method, the urea, ammonium bicarbonate, and ammonia were without material effect on the suspendability.

The stability of the compositions was determined by heating separate ZS-gram aliquots in vented test tubes at 90 C. and periodically determiningthe dieldrin content of the aliquots. The following results were obtained:

Percentage Decomposition of the Dieldrin In this and the following examplesthere was employed a difierential thermal analytical method for ascertaining the stabilities of representative compositions of the invention. The method is based upon the observed fact that chemical decomposition of the toxicant, when it. occurs, is accompanied by evolution or absorption of heat, depending upon whether the chemical reaction is exothermic or endothermic. The occurrence of chemical reaction while a sample of the composition is slowly heated thus is detected by sensitive measurement of heat evolved or absorbed during the heating of the sample.

The apparatus that was used comprised a cylindrical metal block about 3 inches in diameter and 2 inches high. Three holes, each about /8 inch diameter and /2 inch deep, were drilled intothe central area of theupper face of the block. In one hole was positioned a thermocouple. This hole was packed with a sample of the carrier or diluent from the sample of the insecticidal dust or powder that was to be tested. The thermocouple was connected to controlling means whereby the temperature of the block was measured and the rate of heating of the block by suitably positioned electric heaters was controlled to a desired value. The second of the three holes was packed with a further quantity of the carrier or filler, and the third hole was packed with a quantity of the insecticidal dust or powder that was to be tested. Thermocouples in each of these latter two holes were connected together in opposition and then to a recording potentiometer. The potentiometer measured any differences between-the temperatures of thepowders or dusts contained in the second and third holes. While the block was slowly heated, the temperatures of the samples in the second and third holes would increase progressively and equally so long as no chemical or physical change in the'insecticidal dust or powder occurred. If a chemical change or decomposition of the insecticidal dust or powder should occur, the change would be accompanied by either liberation or abaeeaesa sorption of heat, depending uponwhether the reaction was endothermic or exothermic, and with the liberation or absorption ofheat a measurable temperature difference between the samples in the second and third holes would be established. By means of the recording potentiometer the temperature at which such a temperature difierence first became evident was accurately recorded, and the magnitude of the temperature diiferenc'e was measured.

In this example, a dust concentrate composed of by weight dieldrin and by'weight kaolin was tested.

With kaolin alone in one of the two holes containing the interconnected thermocouples and the dust concentrate in the other of these two holes, and with the metal block heated at a constant rate of 2 /2 degrees C. per minute, the pen of the recording potentiometer drew a perfectly straight line on the recording chart (recording temperature difierence 'vs. time, or vs. actual temperature of the block) 'until a block temperature of 96 C. was reached. With further heating there developed a marked positive temperature difference between the two samples which reached its peak at a block temperature of 98-112 C., indicating that an exothermal reaction was occurring in the sample containing the dieldrin. Heating was continued to a maximum temperature of about C. The block was then cooled, the sample withdrawn, and the content of dieldrin in the heated sample was determined by extraction with an organic solvent and measurement of the dieldrin content of the extract by means of infrared absorption. The sample was found to contain 0% dieldrin.

A second sample of thedust concentrate then was tested. This second sample was the same as the first, exceptthat 1% by weight of ammonium bicarbonate was thoroughly blended with the kaolin prior to the admixture of the kaolin and dieldrin. When tested similarly by differential thermal analysis there was observed no evidence of the exothermal reaction which was noted with the first sample. Analysis of the dieldrin content of the heated sample containing ammonium bicarbonate, by the method used for the first sample, showed its dieldrin content still to be 25% by weight.

Example 6 In this example there were compared by the differential a thermal method samples of 25:75 (weight basis) dieldrin- Attapulgus clay dust concentrates containing, respectively,

no additive, ammonium bicarbonate as additive, and urea as additive. The results shown in the following table were observed:

Percent by Weight based on the Attapulgus clay.

7 Example 7 Further samples of 25 :75 (weight basis) dieldrin-kaolin dust concentrates were prepared and tested according to the method described inExample 5. The following results were obtained:

Temperature C.) at Which Exothermic Amount Reaction Was Recorded Additive of Additive,

percent Start of Reaction Maximum Exothermicity none 90-96 98-112. ammonium bi- 1 no reaction recorded no reaction recarbonate. up to C corded up to NH4OH (aq.) 0. 4 .do Do. urea 1 do Do.

Based on the Weight of the clay. b Blended by adding 2% by weight of 20% aqueous ammonium hydroxide to the clay, and after thorough mixing working: in the dieldrin.

Example 8 Using the method described in Example 5, 25:75 (weight basis) dust concentrates containing endrin' as the toxicant were prepared and tested for stability. The results shown in the following table were observed:

Temperature (0.)

at hich Exo- E thermic Reaction Amount Was Recorded Carrier Additive of Additive,- I,

percent Maxi- Start of mum Ex- Reaction. othermicity kaolin none- 31, 72 Do ammonium bi- 1 1 102 124 carbonate. Attapu1gusclay none ca.104, ca. 116 Do. urea 2 ca. 118 ca*.142

e Based on the weight of the carrier.

Example 9 Using the method described in Example 5, 25:75 (Weight basis) Isodrin-kaolin dust concentrates were prepared and tested for stability. The following results were obtained: 1

Temperature C.) at Which Exothermic Amount Reaction Was Recorded Additive of Additive, percent Start of Reaction Maximum Exothermicity none 91. 121. ammonium bi- 1 no reaction recorded no reaction-rev carbonate. up to 180 0. up to n Based on the weight of the kaolin.

Example 10 A series of dieldrin-k'aolin dust concentrates containing 25% by weight dieldrin were prepared. One, which served as a control, contained no additive. Theotliers contained ethanolamine, pyridine, and hexamethylenetetramine, respectively, asstabilizers. The resultsshown in the following table were observed: i

A series of dust concentrates containing diflerent toxicants of the chemical type to which the invention pertains was prepared. With each toxicant there was prepared one lot of dust concentrate containing 25% by weight of the toxicant and 75% by weight of the carrier (clay), and a second lot of an otherwise similar dust concentrate centaining 1% of urea, based on the weight "18 of the clay,- as stabilizer. The dusts were each tested by the'thermal difierential analysis described-in Example 5, with the results shown in the following table:

Temperature C.) at Which Exothermic Reaction Was v Amount Recorded Toxicant Carrier. I of Urea v percent i 1 Start of Maximum Reaction Exothermiclty Toxaphene kaolin none Do a do 1 Ohlordane do. none 90 120 Do do 1 j 140 Heptachlor Attapulgus cla'y none 110 135 Do do 2 140 170 I Chlorinated camphene having a chlorine content of about 67-69%.

It will be seen that in each case the stability of the dust was materially increased by incorporation of a small amount of urea in the composition.

The new and improved compositions of our invention are initially highly toxic to insects and related non-vertebrates" and they retain their toxicity under conditions which prior to our invention were detrimental to the then available insecticidal dusts, wettable powders, and the like containing the toxicants with which we are concerned. The new compositions are non-phytotoxic and are non-injurious to plant life. It will be appreciated by those skilled in the art that there are various specific embodiments of the invention which may be practiced without exceeding. the letter and spirit of the appended claims, and; that it is our intent to claim the invention broadly, as the prior art may permit.

We claim asour invention:

1. A stable solid, pulverulent biocidal composition comprising as toxicant a polyhalogen-substituted organic compound comprising at least one pair of fused carbocyclic rings having from 3 to 7 ring carbon atoms in each of the rings'of said pair and a plurality of atoms ot-halogen substituted on at least one of said carbocyclic rings, as adjuvant a substantially toxicologically inert pulverulent, solid diluent, said diluent normally having an intrinsic acidity represented by a pK less than 0, and an acid-neutralizing agent transfused throughout the composition in an amount at least sufiicient to neutralize the intrinsic acidity of said diluent-to a value not less than 0 and up to 25 by weight of the said diluent.

:2. Aacom'positiorrdefined byclaim 1 comprisingam diluent, clay.

3. A composition defined by claim 2 comprising, as an acid-neutralizing agent, urea.

4. A composition defined by claim 2 comprising, as an acid-neutralizing agent, ammonium bicarbonate.

5. A composition defined by claim 2 comprising, as an acid-neutralizing agent, hexamethylenetetramine.

6. A- composition defined by claim 2 comprising, as an acid-neutralizing agent, ethanolamine.

7. A stable solid, pulverulent biocidal composition comprising as toxicant a polyhalogen-substituted organic compound comprising at least one pair of fused carbocyclic rings having from 3 to 7 ring carbon atoms in each of the rings of said pair and a plurality of atoms of halogen substituted on at least one of said carbocyclic rings and, as adjuvant, a substantially toxicologically inert, pulverulent, solid diluent normally having an 'intrinsic acidity represented by a pK value. less than 0, said diluent having been neutralized to an intrinsic acidity represented by pK value not less than 0 with up to 25 by weight of a neutralizing agent. I

8. A composition defined by claim 7 containing as 19 ,toxicant a compound having a structure represented by the planar structural formula 01001 HCH 01 H 9. A composition defined by claim 7 containing heptachlor as toxicant.

10. A stable solid pulverulent biocidal composition comprising as toxicant a compound having a structure represented by the planar structural formula 01 H V H I 01001 11011 0 01 a I and, as adjuvant, pulverulent clay normally having an intrinsic acidity represented by a pK value less than 0, said clay having been neutralized to an intrinsic acidity represented by a pK value not less than 0 with from 0.05% to of urea, based on the weight of said clay. 11. A stable solid pulverulent biocidal composition comprising as toxicant a compound having a structure represented by the planar structural formula and, as adjuvant, pulverulent clay normally having an intrinsic acidity represented by a pK value less than 0, said clay having been neutralized to an intrinsic acidity represented by a pK value not less than 0 with from 0.05 to 25% of ammonium bicarbonate based on the weight of said clay.

12. A stable solid, pulverulent biocidal composition comprising as toxicant a compound having a structure represented by the planar structural formula and, as adjuvant, clay normally having an intrinsic acidity represented by a pK value less than 0, said clay having been neutralized to an intrinsic acidity represented by a pK not less than 0 with from 0.05% to 25% hexamethylene tetramine based on the weight of said clay.

13. An insecticidal adjuvant comprising pulverulent clay normally having an intrinsic acidity represented by a pK value less than 0 and in intimate admixture there- .with of hexamethylenetetramine in solid state in an amount at least suflicient to neutralize the intrinsic acidity of said clay to a pK value not less than 0 and up to 25 by weight of said clay.

14. A stable insecticide composition comprising dieldrin, a finely divided diluent comprising an attapulgite clay normally having an intrinsic acidity represented by a pK value less than 0, said clay having been neutralized to an intrinsic acidity represented by a pK not less than 0, with from about 0.05% to 25 urea based upon the weight of said clay.

15. A stable insecticide composition comprising dieldrin, a finely divided solid diluent comprising clay normally having an intrinsic acidity represented by a pK References Cited in the file of this patent UNITED STATES PATENTS 2,004,788 Green June 11, 1935 2,538,513 Kenaga Ian. 16, 1951 2,579,297 Buntin Dec. 18, 1951 2,671,043 Gilbert Mar. 2, 1954 FOREIGN PATENTS 624,176 Great Britain May 30, 1949 OTHER REFERENCES Knissetf: Chem. Abstr., vol. 26 (1932), p. 3163. 127l 3ussart: Soap and Sanitary Chem., August 1948, p.

Roark: A Digest of Infor. on Chlordane, U. S. Dept. of Agr., Bur. of But. and Plant Quarantine, Agr. Res. Adm., publ. E-817 (April 1951) p. 11.

Roark: A Digest of Infor. on Toxaphene, U. S. Dept. of Agr., Agr. Res. Adm., Bur. of But. and Plant Quarantine, publ. E-802 (1950), p. 6. 

1. A STABLE SOLID, PULVERULENT BIOCIDAL COMPOSITION COMPRISING AS TOXICANT A POLYHALOGEN-SUBSTITUTED ORGANIC COMPOUND COMPRISING AT LEAST ONE PAIR OF FUSED CARBOCYCLIC RINGS HAVING FROM 3 TO 7 RING CARBON ATOMS IN EACH OF THE RINGS OF SAID PAIR AND A PLURALITY OF ATOMS OF HALOGEN SUBSTITUTED ON AT LEAST ONE OF SAID CARBOCYCLIC RINGS, AS ADJUVANT A SUBSTANTIALLY TOXICOLOGICALLY INERT PULVERULENT, SOLID DILUENT, SAID DILUENT NORMALLY HAVING AN INTRINSIC ACIDITY REPRESENTED BY A PKA LESS THAN 0, AND AN ACID-NEUTRALIZING AGENT TRANSFUSED THROUGHOUT THE COMPOSITION IN AN AMOUNT AT LEAST SUFFICIENT TO NEUTRALIZE THE INTRINSIC ACIDITY OF SAID DILUENT TO A VALUE NOT LESS THAN 0 AND UP TO 25% BY WEIGHT OF THE SAID DILUENT. 